Patent GB-1071768-A (GB)
Title: Antistatic compositions derived from polyphenylene oxides
IPC: C08J7/044
Filed: 1964-10-09
Abstract: Ionic derivatives of polyphenylene ethers which basic polyphenylene ether consists of at least 10 repeating structural units of the formula <FORM:1071768/C3/1> wherein the oxygen atom of one unit is connected to the benzene nucleus of the adjoining unit, Q is hydrogen or a monovalent substituent selected from aliphatic hydrocarbon or halohydrocarbon radicals which are free of a tertiary a -carbon atom. Q1 and Q11 are the same as Q and in addition halogen, arylhydrocarbon and haloarylhydrocarbon radicals, hydrocarbonoxy radicals having at least two carbon atoms and halohydrocarbonoxy radicals having at least two carbon atoms and being free of an aliphatic tertiary a carbon atom are prepared, e.g. by reacting the corresponding phenol with oxygen in the presence of an amine and a cuprous salt soluble in the amine and capable of existing in the cupric state followed by substitution of the relevant ionic groups. Examples of ionic derivatives are (a) sulphonic acid derivatives prepared by reacting polyphenylene oxide with chlorosulphonic acid or SO3, (b) nitroso, hydroxylamino or amino derivatives prepared by reaction of polyphenylene oxides with nitric acid followed by reduction, the amino derivatives if desired being alkylated to remove the hydrogen atoms of the amine groups, (c) amino derivatives prepared by amination of polyphenylene oxides containing Cl, Br or I attached to the aromatic nucleus, which amino derivatives may be diazotized to yield diazonium groups which may be replaced by halogens, CN, CNO, CNS, PCl2 and AsCl2 which in turn may be converted to e.g. CN to COOH, CN to CH2NH2, PCl2 to PO2H2 and PO3H2, AsCl2 to AsO2H2 and AsO3H2, (d) halomethyl derivatives prepared by reaction of a polyphenylene oxide with free halogen or sulphuryl chloride or bromide or bromosuccinimide followed if desired by reaction with alkali metal salts to replace the halogen group by the anion of the salt, e.g. alkali metal cyanides, alkali metal malonic esters or alkali metal mercaptans or the halomethyl polymer may be reacted with trialkyl phosphites followed by hydrolysis to the corresponding phosphonic acids.  The above ionic derivatives may be dissolved in inert organic solvents and coated on to or used to impregnate various substrates (see Divisions B2 and D1).ALSO:Nylon tricot slips may be rendered antistetic by treating them with a solution in an organic solvent of quaternery ammoniated poly2,6-dimethyl-1,4-phenylene oxide which contains 3 NMe3+ Cl groups per 10 aryl units.ALSO:Substrates are rendered antistatic by coating them with ionic derivatives of a polyphenylene ether which basic polyphenylene ethers consists of at least 10 repeating structural units of the formula: <FORM:1071768/B1-B2/1> wherein the oxygen atom of one unit is connected to the benzene nucleus of the adjoining unit, Q is hydrogen or aliphatic hydrocarbon or halohydrocarbon radicals free of a tertiary a -carbon atom, Q\sv and Q" are the same as Q and in addition halogen, arylhydrocarbon or haloarylhydrocarbon radicals of hydrocarbonoxy or halohydrocarbonoxy radicals containing at least two carbon atom and being free of an aliphatic, tertiary a -carbon atom. The ionic groups are suitably nuclear substituent groups and may be nitro, amino, diazonium, nitrile, carboxyl, quaternary ammonium, -PX2, -ASX2, wherein X is halogen, -SO3H, -PO3H2, -ASO2H2 and ASO3H2. The ionic derivative is normally dissolved in a solvent e.g. tetrahydrofuran-methanol, ketone-alcohol or ketone-water mixtures and applied to the substrate by dipping, painting or spraying.  Examples describe the coating onto polystyrene, polypropylene, polycarbonates, polymethylmethacrylate, polyformaldehyde, polyphenylene oxide, polyethylene terephthalate and paper of a sulphonated poly-2,6-dimethyl-1, 4-phenylene oxide, a quaternary ammoniated poly-2,6-dimethyl-1, 4-phenylene oxide and a sodium phosphonated poly-2,6-dimethyl-1,4-phenylene oxide.